JP6969092B2 - Adhesive sheet for conductive member, laminated body of conductive member and image display device - Google Patents

Description

The present invention relates to an adhesive sheet for conductive members, a laminated body of conductive members using the adhesive sheet, and the like. In particular, in an image display device using an image display panel such as a plasma display (PDP), a liquid crystal display (LCD), an organic EL display (OLED), an inorganic EL display, an electrophoresis display (EPD), and an interference modulation display (IMOD). The present invention relates to an adhesive sheet for a conductive member suitable for bonding a conductive member such as a transparent conductive layer.

Image display devices such as personal computers, mobile terminals (PDAs), game consoles, televisions (TVs), car navigation systems, touch panels, pen tablets, etc., such as plasma displays (PDPs), liquid crystal displays (LCDs), organic EL displays (OLEDs). ), Inorganic EL display, electrophoretic display (EPD), interference modulation display (IMOD), and other image display devices that use flat or curved image display panels to ensure visibility and prevent damage. No gaps are provided between the constituent members, and the respective constituent materials are bonded and integrated with a pressure-sensitive adhesive sheet or a liquid pressure-sensitive adhesive.

For example, in an image display device having a structure in which a touch panel is inserted between the visible side of a liquid crystal module and a surface protection panel, an adhesive sheet or a liquid adhesive is used between the surface protection panel and the visible side of the liquid crystal module. Is arranged, and the touch panel and other constituent members, for example, the touch panel and the liquid crystal module, and the touch panel and the surface protection panel are bonded and integrated.

The touch panel is usually formed of a metal oxide such as tin-doped indium oxide (ITO), indium-gallium-zinc composite oxide (IGZO), or Ga-doped zinc oxide (GZO), or a metal material such as silver, copper, or molybdenum. It is provided with an upper electrode plate and a lower electrode plate having a transparent conductive layer formed of fine wiring, silver nanowires, carbon nanotubes and the like. Further, in order to aggregate and communicate the position information of the finger, touch pen, etc. detected by the transparent conductive layer, a conductor pattern (wiring pattern) formed of a metal material is formed between the transparent conductive layer and the control means such as an IC. It is formed. The transparent conductive layer or conductor pattern formed from these various materials is usually fixed so that the surface is in contact with the adhesive. The transparent conductive layer and the conductor pattern are vulnerable to corrosion, and may be corroded by the outgas of the adhesive material or the acid component derived from the elution component in a high temperature or moist heat environment, and may be broken in some cases.

Therefore, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet for attaching a metal containing benzotriazole and / or a derivative thereof as a metal corrosion inhibitor.

Further, for example, Patent Document 2 describes a pressure-sensitive adhesive composition containing an acrylic polymer and a cross-linking agent, which are composed of an alkoxyalkyl acrylate and an acrylic monomer having a crosslinkable functional group as essential components, and are contained in the acrylic polymer. Discloses a pressure-sensitive adhesive composition that is substantially free of carboxyl group-containing monomers. According to such a pressure-sensitive adhesive composition, yellowing is suppressed by using a specific amount of an aliphatic isocyanate cross-linking agent and an amine-based compound containing a plurality of hydroxyl groups, and the acrylic polymer has a cross-linked structure. Thereby, it is disclosed that the foaming resistance and peeling resistance under high temperature can be satisfied even if the carboxyl group-containing monomer component is not contained.

Japanese Unexamined Patent Publication No. 2006-45315 Japanese Unexamined Patent Publication No. 2009-079203

Since the constituent members used in the image display device include members that generate gas (also referred to as “outgas”) over time in a high temperature and high humidity environment, the constituent members of these image display devices are adhered to each other. When bonded with a sheet, the pressure-sensitive adhesive sheet must also have foaming reliability that can sufficiently withstand the gas pressure of outgas.

The double-sided pressure-sensitive adhesive sheet containing the metal corrosion inhibitor of Patent Document 1 has a problem that the metal corrosion inhibitor foams in a durability test of irradiating with ultraviolet rays and deteriorates optical characteristics.

According to the pressure-sensitive adhesive composition of Patent Document 2, it is said that even an acrylic polymer containing no carboxyl group-containing monomer such as acrylic acid can satisfy foaming resistance and peeling resistance at high temperatures. However, since it is not possible to prevent the infiltration of water, which is a cause of corrosion, into the adhesive, it is not always satisfactory from the viewpoint of preventing metal corrosion.

Therefore, an object to be solved by the present invention is to provide a pressure-sensitive adhesive sheet for a conductive member, which does not corrode the conductive member and has foam resistance reliability and good curing characteristics. More specifically, even if they are directly bonded to the conductive layer surface of the transparent conductive layer or a conductor pattern (wiring pattern) formed of a metal material, they do not corrode and are insulated from the conductive layer surface of the transparent conductive layer. It is an object of the present invention to provide an adhesive sheet for a conductive member which does not corrode the transparent conductive layer even when bonded via a protective film (passive film).

In the present invention, (meth) have a pressure-sensitive adhesive layer including the pressure-sensitive adhesive composition containing an acrylic copolymer and 1,2,3-triazole, a composition wherein the adhesive composition has a photocurable The main feature is that there is.

The pressure-sensitive adhesive sheet for a conductive member of the present invention can have corrosion resistance to the conductive member, foaming reliability as a pressure-sensitive adhesive sheet, and good curing properties. Therefore, the pressure-sensitive adhesive sheet for conductive members of the present invention is suitable as a pressure-sensitive adhesive sheet for bonding various conductive members such as a transparent conductive layer and / or a conductive member having a conductor pattern formed of a metal material containing copper or silver. Can be used. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.

In Examples described later, it is a figure for demonstrating the evaluation test method of corrosion resistance reliability, (A) is the top view of the ITO pattern of the ITO glass substrate for oxidation deterioration prevention evaluation, or copper for corrosion resistance evaluation. Top view of the copper pattern of the glass substrate, (B) is a top view showing the state where the pressure-sensitive adhesive sheet is coated on the ITO glass substrate for oxidation deterioration prevention evaluation, or the pressure-sensitive adhesive sheet is placed on the copper glass substrate for corrosion resistance evaluation. A top view showing a coated state, (C) is a cross-sectional view of a sample for evaluating oxidative deterioration prevention, and (D) is a cross-sectional view of a sample for evaluating corrosion resistance reliability.

Hereinafter, an example of the embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<Adhesive sheet for conductive members>
The pressure-sensitive adhesive sheet for conductive members (hereinafter, also abbreviated as “the present pressure-sensitive adhesive sheet”) according to an example of the embodiment of the present invention comprises a (meth) acrylic (co) polymer and 1,2,3-triazole. It has a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition contained therein.

The pressure-sensitive adhesive layer may be a single layer or a multilayer layer, and in the case of a multilayer layer, another layer such as a so-called base material layer may intervene. When the pressure-sensitive adhesive layer has a multi-layer structure having another layer, it is preferable that the surface layer of the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition.
When the pressure-sensitive adhesive sheet has multiple layers, the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is not limited, but is preferably 10% or more, more preferably 30% or more, based on the total thickness of the pressure-sensitive adhesive sheet. , More preferably 50% or more. When the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is within the above range, corrosion resistance, foaming reliability, and curing characteristics for the conductive member are good, which is preferable.
In the present invention, "(co) polymer" means to include homopolymers and copolymers, and "(meth) acrylate" means to include acrylates and methacrylates.

[Adhesive composition]
The pressure-sensitive adhesive composition used for the present pressure-sensitive adhesive sheet (hereinafter, abbreviated as “the present composition”) contains a (meth) acrylic (co) polymer and 1,2,3-triazole.
The composition may further contain a phosphite ester compound, a cross-linking agent, a photopolymerization initiator, an antioxidant, and other components.
The present composition is preferably a photocurable composition.

((Meta) acrylic (co) polymer)
Examples of the (meth) acrylic (co) polymer include a homopolymer of an alkyl (meth) acrylate and a copolymer obtained by polymerizing this with a monomer component having copolymerizability. From among alkyl (meth) acrylates and carboxyl group-containing monomers, hydroxyl group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, amide group-containing monomers, and other vinyl monomers that can be copolymerized with the alkyl (meth) acrylate. Examples thereof include a copolymer containing any one or more selected monomers as a constituent unit.
The (meth) acrylic (co) polymer can be produced by a conventional method using the monomers and the like exemplified below using a polymerization initiator, if necessary.

When the (meth) acrylic (co) polymer is a copolymer containing a carboxyl group-containing monomer as a constituent unit, the (meth) acrylic (co) polymer contains a carboxyl group from the viewpoint of obtaining excellent adhesive physical properties. The monomer is preferably contained in an amount of 1.2 to 15% by mass, more preferably 1.5% by mass or more or 10% by mass or less, and further preferably 2.0% by mass or more or 8% by mass or less.

As an example of a more specific (meth) acrylic (co) polymer, a linear or branched alkyl (meth) acrylate having 4 to 18 carbon atoms in the side chain (hereinafter, also referred to as “copolymerizable monomer A”). And a copolymer composed of any one or more monomer components selected from the following group that can be copolymerized with this.

Carboxyl group-containing monomer (hereinafter also referred to as "copolymerizable monomer B")
-Macromonomer (hereinafter also referred to as "copolymerizable monomer C")
-A (meth) acrylate having 1 to 3 carbon atoms in the side chain (hereinafter, also referred to as "copolymerizable monomer D").
Hydroxy group-containing monomer (hereinafter also referred to as "copolymerizable monomer E")
-Other vinyl monomers (hereinafter also referred to as "copolymerizable monomer F")

Further, as an example of the (meth) acrylic (co) polymer, a copolymer composed of (a) a copolymerizable monomer A and a monomer component containing the copolymerizable monomer B and / or the copolymerizable monomer C. It is composed of a coalesced or a monomer component containing (b) a copolymerizable monomer A, a copolymerizable monomer B and / or a copolymerizable monomer C, and a copolymerizable monomer D and / or a copolymerizable monomer E. Copolymers can also be mentioned as a particularly suitable example.

Examples of the linear or branched alkyl (meth) acrylate (copolymerizable monomer A) having 4 to 18 carbon atoms in the side chain include n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl (meth). ) Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (Meta) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) Acrylate, Undecyl (meth) acrylate, Lauryl (meth) acrylate, Tridecyl (meth) acrylate, Tetradecyl (meth) acrylate, Cetyl (meth) acrylate, Stearyl (meth) acrylate, Isostearyl (meth) acrylate, Behenyl (meth) acrylate , Isobornyl (meth) acrylate, 3,5,5-trimethylcyclohexane (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) ) Acrylate and the like can be mentioned. These may be used alone or in combination of two or more.

The copolymerizable monomer A is preferably contained in an amount of 30% by mass or more and 90% by mass or less, particularly 35% by mass or more or 88% by mass or less, and particularly 40% by mass, in all the monomer components of the copolymer. It is more preferably contained in the above range or in the range of 85% by mass or less.

Examples of the carboxyl group-containing monomer (copolymerizable monomer B) include (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2 -(Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxy Examples thereof include ethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, and itaconic acid. These may be one kind or a combination of two or more kinds. In addition, "(meth) acrylic" means to include acrylic and methacrylic. Similarly, "(meth) acryloyl" means to include acryloyl and methacryloyl.

The copolymerizable monomer B is 1.2% by mass or more and 15% by mass or less in all the monomer components of the copolymer, especially 1.5% by mass or more or 10% by mass or less from the viewpoint of obtaining excellent adhesive properties. Above all, it is particularly preferable that the content is in the range of 2% by mass or more or 8% by mass or less.

The macromonomer (copolymerizable monomer C) is a monomer having 20 or more carbon atoms in the side chain when it becomes a (meth) acrylic (co) polymer by polymerization. By using the copolymerizable monomer C, the (meth) acrylic (co) polymer can be used as a graft copolymer. Therefore, the characteristics of the main chain and the side chain of the graft copolymer can be changed by selecting and blending the copolymerizable monomer C and other monomers.

As the macromonomer (copolymerizable monomer C), it is preferable that the skeleton component is composed of an acrylic polymer or a vinyl polymer. Examples of the skeleton component of the macromonomer include those exemplified for the above-mentioned copolymerizable monomer A, the above-mentioned copolymerizable monomer B, the below-mentioned copolymerizable monomer D, the below-mentioned copolymerizable monomer E, and the like. Can be used alone or in combination of two or more.

The macromonomer has a radical polymerizable group or a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group and a thiol group. The macromonomer preferably has a radically polymerizable group that can be copolymerized with another monomer. One or two or more radically polymerizable groups may be contained, and one of them is particularly preferable. When the macromonomer has a functional group, it may contain one or more functional groups, and one of them is particularly preferable. Further, the radically polymerizable group and the functional group may be contained in either one or both.

The number average molecular weight of the copolymerizable monomer C is preferably 500 to 20,000, particularly preferably 800 or more or 8000 or less, and particularly preferably 1000 or more or 7,000 or less.
As the macromonomer, a generally manufactured one (for example, a macromonomer manufactured by Toagosei Co., Ltd.) can be appropriately used.
The copolymerizable monomer C is 5% by mass or more and 30% by mass or less, particularly 6% by mass or more or 25% by mass or less, and particularly 8% by mass or more or 20% by mass or less in all the monomer components of the copolymer. It is preferably contained in a range.

Examples of the (meth) acrylate (copolymerizable monomer D) having 1 to 3 carbon atoms in the side chain include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and i-propyl (meth). ) Acrylate and the like can be mentioned. These may be one kind or a combination of two or more kinds.

The copolymerizable monomer D is preferably contained in 0% by mass or more and 70% by mass or less in all the monomer components of the copolymer, particularly 3% by mass or more or 65% by mass or less, and particularly 5% by mass or more. Alternatively, it is more preferably contained in the range of 60% by mass or less.

Examples of the hydroxyl group-containing monomer (copolymerizable monomer E) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates can be mentioned. These may be one kind or a combination of two or more kinds.

The copolymerizable monomer E is preferably contained in 0% by mass or more and 30% by mass or less in all the monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and particularly 0% by mass or more. Alternatively, it is more preferably contained in the range of 20% by mass or less.

Examples of the other vinyl monomer (copolymerizable monomer F) include compounds having a vinyl group in the molecule, excluding the copolymerizable monomers A to E. Such compounds include functional monomers having a functional group such as an amide group and an alkoxylalkyl group in the molecule, polyalkylene glycol di (meth) acrylates, and vinyl such as vinyl acetate, vinyl propionate and vinyl laurate. Examples thereof include ester monomers and aromatic vinyl monomers such as styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene and other substituted styrenes. These may be one kind or a combination of two or more kinds.

The copolymerizable monomer F is preferably contained in 0% by mass or more and 30% by mass or less in all the monomer components of the copolymer, particularly 0% by mass or more or 25% by mass or less, and particularly 0% by mass or more. Alternatively, it is more preferably contained in the range of 20% by mass or less.

In addition to those listed above, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, -3,4-epoxybutyl (meth) acrylate and the like. Epoxy group-containing monomer; Amino group-containing (meth) acrylic acid ester-based monomer such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, N-t-butyl (meth) acrylamide, N- Monomers containing amide or imide groups such as methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, maleic acid amide, maleimide, etc .; vinylpyrrolidone , Vinyl pyridine, vinyl carbazole and other heterocyclic basic monomers can also be appropriately used as needed.

The most typical examples of (meth) acrylic (co) polymers are, for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isostearyl (meth) acrylate, butyl ( Monomeric component (a) such as meta) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, (meth) acrylic acid having a carboxyl group, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( Meta) Acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxy Monomer components (b) such as propylmaleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, organic functional groups, etc. Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, monomethyl maleate, monomethyl itaconate, vinyl acetate, glycidyl (meth) acrylate, (meth) acrylamide. , (Meta) acrylic acid ester copolymer obtained by copolymerizing a monomer component (c) such as (meth) acrylonitrile, fluorinated (meth) acrylate, and silicone (meth) acrylate.

The mass average molecular weight of the (meth) acrylic (co) polymer is preferably 100,000 or more and 1.5 million or less, particularly preferably 150,000 or more or 1.3 million or less, and particularly preferably 200,000 or more or 1.2 million or less.

When it is desired to obtain a pressure-sensitive adhesive composition having a high cohesive force, the mass average molecular weight of the (meth) acrylic (co) polymer is 700,000 or more and 1.5 million from the viewpoint that the larger the molecular weight is, the more the cohesive force is obtained by the entanglement of the molecular chains. Hereinafter, it is particularly preferable that the amount is 800,000 or more or 1.3 million or less. On the other hand, when it is desired to obtain a pressure-sensitive adhesive composition having high fluidity and stress relaxation property, the mass average molecular weight is preferably 100,000 or more and 700,000 or less, particularly preferably 150,000 or more or 600,000 or less.
On the other hand, when a solvent is not used when molding an adhesive sheet or the like, it is difficult to use a polymer having a large molecular weight. Therefore, the mass average molecular weight of the (meth) acrylic (co) polymer is 100,000 or more and 700,000. Below, it is particularly preferable that it is 150,000 or more or 600,000 or less, and particularly preferably 200,000 or more or 500,000 or less.

(Metal corrosion inhibitor)
The composition contains 1,2,3-triazole.
1,2,3-triazole has a function as a metal corrosion inhibitor for the conductive layer of the conductive member. Since 1,2,3-triazole is excellent in copper corrosion resistance to copper and foaming reliability as an adhesive sheet, this composition containing 1,2,3-triazole is a transparent conductive layer and copper. It can be suitably used as a conductive member having a conductor pattern (wiring pattern) formed of a metal material containing. The reason is that a protective film in which copper atoms and 1,2,3-triazole molecules are chemically bonded is formed on the surface of a conductor pattern made of a metal material containing copper to prevent corrosion. This is because it is inferred. Further, even in a conductive member having a conductor pattern formed of a metal material containing silver, the effect of the protective film by 1,2,3-triazole can be similarly exerted.

It should be noted that 1,2,4-triazole exists as an isomer of 1,2,3-triazole. The 1,2,4-triazole is a solid having a melting point of about 120 ° C., while the 1,2,3-triazole has a melting point of about 20 ° C. and is almost in a liquid state at room temperature. Therefore, 1,2,3-triazole has excellent dispersibility when mixed in the pressure-sensitive adhesive composition, can be mixed uniformly, and has excellent advantages such as easy masterbatch.

In this composition, from the viewpoint of bleed-out of the metal corrosion inhibitor and the effect of preventing metal corrosion, 1,2,3-triazole is 0. It is preferably contained in a proportion of 01 parts by mass or more and 5 parts by mass or less, particularly 0.1 parts by mass or more or 1 part by mass or less, and among them, 0.2 parts by mass or more or 0.5 parts by mass or less. It is even more preferable to be done.

In addition, 1,2,4-triazole may be used in combination with 1,2,3-triazole in this composition.

(Phosphite ester compound)
The present composition can further contain a phosphite ester compound.
Not only is the phosphite ester compound not corrosive in itself, but it can also stabilize acid components such as carboxyl groups. Therefore, by blending the phosphite ester compound with the present composition containing a predetermined (meth) acrylic (co) polymer, even if the present composition contains an acid component, the conductive member which is an adherend. It is possible to prevent oxidative deterioration of the composition, and of course, when the present composition does not contain an acid component, oxidative deterioration of the conductive member as an adherend can be prevented.
Therefore, if the pressure-sensitive adhesive sheet is formed from the present composition containing a phobic acid ester compound, a conductive member (typically a transparent conductive layer containing ITO and / or a conductor pattern formed of a metal material containing copper or silver) can be formed. It has corrosion resistance and reliability for the conductive member), and can prevent oxidative deterioration of the conductive member. Therefore, for example, it can be suitably used as an adhesive sheet for an image display device having a touch panel.

The phosphite ester compound that can be contained in this composition is not limited. Of these, the phosphite ester compound represented by the following formula (1) is preferable.

Equation (1) ... P [-OR] ₃
(Rs in the formula are hydrocarbons, and specific examples thereof include substituted or unsaturated aromatics, alicyclics and alkyl groups. A plurality of Rs may be the same or different from each other and are adjacent to each other. The plurality of Rs may be coupled to each other to form a saturated or unsaturated ring structure.)
Further, it may be a compound containing two or more structural units represented by the above formula (1).

As a result of blending various phosphite ester compounds represented by the above formula (1) with the present composition containing a predetermined (meth) acrylic (co) polymer and 1,2,3-triazole, any sub. It was confirmed that the phosphoric acid ester compound also showed an oxidative deterioration preventing effect, and it was confirmed that the phosphoric acid ester compound was particularly excellent in the oxidative deterioration preventing effect on the transparent conductive layer containing ITO.

Examples of the phosphite ester compound contained in this composition include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, tristearyl phosphite, triethyl phosphite, and tris phosphite (triethyl phosphite). 2-Ethylhexyl), Tridecyl phosphite, Trilauryl phosphite, Tristris phosphite (Tridecyl), Trioleyl phosphite, Diphenyl phosphite (2-ethylhexyl), Diphenyl monodecyl phosphite, Diphenyl phosphite Mono (tridecyl), tetraphenyldipropylene dipropylene glycol diphosphite, tetraphenyl (tetratridecyl) pentaerythritol tetraphosphite, tetra (C12-C15 alkyl) -4,4-isopropyridene diphenyldiphosphite, subphosphoric acid Tris acid (2,4-di-t-butylphenyl), Tris phosphite (4-nonylphenyl), 3,9-bis (nonylphenoxy) -2,4,8,10-tetraoxa-3,9- Diphosphaspiro [5,5] undecane, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (decyloxy) -2,4,8,10-Tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (tridecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5,5] Undecane, 3,9-bis (stearyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] Undecane, 3,9-bis (2,6-di-) tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (2,4-di-tert-butylphenoxy)- 2,4,8,10-Tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis {2,4-bis (1-methyl-1-phenylethyl) phenoxy} -2,4 8,10-Tetraoxa-3,9-diphosphaspiro [5,5] undecane, 2,2'-methylenebis (4,6-di-tert-butyl-1-phenyloxy) phosphite, 4,4'-isopropyri Dendiphenol C12-15 Alcohol Phosphite, Distealyl Pentaerythritol Diphosphite, 2,4,8,10-Tetrakiss (1,1-dimethylethyl) -6- {(2-Ethylhexyl) oxy} -12H-dibenzo [d, g] [1,3,2] dioxaphosphosine, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6- (Tridecyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphosin, 1,1'-biphenyl-4,4'-diylbis [bis phosphite (2,4-) Di-t-butylphenyl)], hydrogenated bisphenol A / pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, diethyl phosphite, bis (2-ethylhexyl) phosphite, dilauryl phosphite, phosphite Examples thereof include acid dioleyl and diphenyl phosphite.

Among them, as the phosphorous acid ester compound contained in the present composition, for example, considering the compatibility with the present composition, the aliphatic phosphite ester (for example, the phosphorous acid ester compound of Example 2-2 is sub-phosphorus acid ester compound. Tridecyl phosphate and 3,9-bis (decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane of Examples 2-3) are preferable. Further, in consideration of hydrolysis resistance, an aromatic phosphite ester (for example, tris phosphite (2,4-di-t-butylphenyl) as the phosphite ester compound of Example 2-1) Is preferable. Further, considering the balance between solubility and hydrolysis resistance, a phosphite ester having both an aliphatic ester group such as diphenylmono (tridecyl) phosphite and an aromatic ester group is preferable.

In the present composition, the content ratio of the phosphite ester compound does not impair the adhesive performance, and from the viewpoint of more effectively suppressing the oxidative deterioration of the conductive member such as ITO, the (meth) acrylic (co) ^{The phosphite ester compound is preferably contained in a proportion of 0.0001 (1 × 10 -4} ) parts or more and 2.0 parts by mass or less with respect to 100 parts by mass of the polymer, and more than 0.0005 parts by mass. Alternatively, it is more preferably contained in a proportion of 0.8 parts by mass or less, of which 0.001 parts by mass or more or 0.7 parts by mass or less, particularly 0.01 parts by mass or more or 0.6 parts by mass or less. ..

(Other metal corrosion inhibitors)
In addition to 1,2,3-triazole and phosphite ester compounds, other metal corrosion inhibitors such as 1,2,4-triazole, benzotriazole and derivatives thereof may be used in combination with this composition.

(Crosslinking agent)
The present composition may contain a cross-linking agent, if necessary.
For example, as a method for cross-linking the above-mentioned (meth) acrylic (co) polymer, cross-linking that can chemically bond with a reactive group such as a hydroxyl group or a carboxyl group introduced into the (meth) acrylic (co) polymer. A method of adding an agent and reacting by heating or curing, or adding a reaction initiator such as a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups as a cross-linking agent and a photopolymerization initiator, and irradiating with ultraviolet rays. Examples thereof include a method of cross-linking by means of the like. Above all, a cross-linking method by irradiation with light such as ultraviolet rays is preferable from the viewpoint that the polar functional groups such as the carboxyl group in the present composition are not consumed by the reaction and the high cohesive force and the adhesive physical characteristics derived from the polar components can be maintained.

Examples of the cross-linking agent include (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, amide group and N-substituted. Examples thereof include a cross-linking agent having at least one cross-linking functional group selected from a (meth) acrylamide group and an alkoxysilyl group, and one or a combination of two or more may be used. The crosslinkable functional group may be protected by a deprotectable protecting group.

Of these, polyfunctional (meth) acrylates are preferable from the viewpoint of ease of control of the cross-linking reaction.
Examples of such polyfunctional (meth) acrylates include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonandiol di (meth) acrylate, and poly. Alkylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri. Pentaerythritol Penta (meth) acrylate, trimethylolpropantri (meth) acrylate, tris (acryloxyethyl) isocyanurate and other UV-curable polyfunctional monomers, as well as polyester (meth) acrylate, epoxy (meth) acrylate, Examples thereof include polyfunctional acrylic oligomers such as urethane (meth) acrylate and polyether (meth) acrylate, and polyfunctional acrylamide.

Examples of the cross-linking agent having two or more kinds of cross-linking functional groups include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, -3,4-epoxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Epoxide group-containing monomers such as meta) acrylate glycidyl ether; 2-isocyanatoethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, (meth) acrylic acid 2- (0- [ Monomerics containing isocyanate groups or blocked isocyanate groups such as 1'-methylpropyrideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate; vinyltrimethoxysilane, Vinyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2- (aminoethyl) -3 -Various silane coupling agents such as aminopropylmethyldimethoxysilane and 3-isocyanatepropyltriethoxysilane can be mentioned.

A cross-linking agent having two or more kinds of cross-linking functional groups has a structure in which one of the functional groups is reacted with a (meth) acrylic (co) polymer and bonded to the (meth) acrylic (co) polymer. good. By adopting such a structure, a double-bonding crosslinkable functional group such as a (meth) acryloyl group or a vinyl group can be chemically bonded to the (meth) acrylic (co) polymer. Further, by binding the cross-linking agent to the (meth) acrylic (co) polymer, it tends to be possible to suppress the bleed-out of the cross-linking agent and the unexpected plasticization of the present pressure-sensitive adhesive sheet. Further, since the cross-linking agent is bonded to the (meth) acrylic (co) polymer, the reaction efficiency of the photocrosslinking reaction is promoted, so that a cured product having higher cohesive force tends to be obtained. ..

The composition may further contain a monofunctional monomer that reacts with the crosslinkable functional group of the crosslinker. Examples of such monofunctional monomers include alkyl (meth) acrylates such as methyl acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyalkylene glycol (meth) acrylate and the like. Hydroxyl-containing (meth) acrylate; (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid. , 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid , Maleic acid, Itaconic acid and other carboxyl group-containing monomers; Maleic anhydride, Itaconic acid anhydride and other acid anhydride group-containing monomers; Tetrahydrofurfuryl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and other ether group-containing monomers ( Meta) acrylate; (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloyl morpholine, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, phenyl (meth) acrylamide, N-methoxy Examples thereof include (meth) acrylamide-based monomers such as methyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide.
Above all, from the viewpoint of improving the adhesion to the adherend and the effect of suppressing moist heat bleaching, it is preferable to use a hydroxyl group-containing (meth) acrylate or a (meth) acrylamide-based monomer.

The content of the cross-linking agent is 0.01 or more and 10 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic (co) polymer from the viewpoint of balancing the flexibility and the cohesive force of the present composition. In particular, it is preferably 0.05 parts by mass or more or 8 parts by mass or less, and particularly preferably 0.1 parts by mass or more or 5 parts by mass or less.
When the present pressure-sensitive adhesive sheet has multiple layers, the content of the cross-linking agent may exceed the above range for the intermediate layer and the base material layer among the layers constituting the pressure-sensitive adhesive sheet. The content of the cross-linking agent in the intermediate layer and the base material layer is preferably 0.01 or more and 40 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic (co) polymer. Above all, it is particularly preferable that it is 1 part by mass or more or 30 parts by mass or less, and more than 2 parts by mass or 25 parts by mass or less.

(Photopolymerization initiator)
When cross-linking by light irradiation, it is preferable to contain a photopolymerization initiator.
Radical generation mechanisms by photopolymerization initiators are roughly classified into two types: the α cleavage type, which cleaves and decomposes its own single bond to generate radicals, and the hydrogen extraction, which excites hydrogen from compounds in the system to generate radicals. There is a type. Among these, it is preferable to use a hydrogen abstraction type photo-crosslink initiator.

Above all, when an organic cross-linking agent having a (meth) acryloyl group is used as the cross-linking agent, it is particularly preferable to further add a photopolymerization initiator. This is because radicals are generated by light irradiation and serve as the starting point of the polymerization reaction in the system.

As the photopolymerization initiator, currently known ones can be appropriately used. Of these, a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of ease of control of the crosslinking reaction.
On the other hand, a photopolymerization initiator that is sensitive to light having a wavelength longer than 380 nm is preferable because it can obtain high photoreactivity and the sensitive light easily reaches the deep part of the pressure-sensitive adhesive sheet.

Photopolymerization initiators are roughly classified into two types according to the radical generation mechanism: a cleavage-type photopolymerization initiator that can generate radicals by cleaving and decomposing a single bond of the photopolymerization initiator itself, and a photo-excited initiator. It is roughly classified into a hydrogen abstraction type photopolymerization initiator capable of forming an excitation complex with a hydrogen donor in the system and transferring the hydrogen of the hydrogen donor.

Of these, the cleavage-type photopolymerization initiator decomposes to another compound when a radical is generated by light irradiation, and once excited, it loses its function as a cross-linking initiator. Therefore, it is preferable because it does not remain as an active species in the pressure-sensitive adhesive after the cross-linking reaction is completed and there is no possibility of causing unexpected photodegradation or the like in the pressure-sensitive adhesive material.
On the other hand, the hydrogen abstraction type photopolymerization initiator does not generate a decomposition product like a cleaved type photopolymerization initiator during a radical generation reaction by irradiation with active energy rays such as ultraviolet rays, so that it does not easily become a volatile component after the reaction is completed and is adhered. It is useful in that it can reduce damage to the body.

The cleavage-type photopolymerization initiator is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, in that it is highly sensitive to light and becomes a decomposition product and decolorizes after the reaction. Acylphosphine oxides such as 6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide Photopolymerization initiators are preferred.

Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (meth). ) Acryloyloxybenzophenone, 4- [2-((meth) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4'-methoxybenzophenone, 2-benzoyl methyl benzoate, methyl benzoylate, bis (2-) Phenyl-2-oxoacetic acid) Oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2 , 4-Dimethylthioxanthone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, phenylquinone and derivatives thereof.
Among these, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (meth) acryloyloxybenzophenone, 4-[ 2-((Meta) acryloyloxy) ethoxy] benzophenone, 4- (meth) acryloyloxy-4'-methoxybenzophenone, 2-benzoyl methyl benzoate, methyl benzoyl formate are preferred.

As the photopolymerization initiator listed above, any one of them or a derivative thereof may be used, or two or more of them may be used in combination.
Further, it is also possible to use a sensitizer in addition to the photopolymerization initiator. The sensitizer is not particularly limited, and any sensitizer used as a photopolymerization initiator can be used without any problem. Examples thereof include aromatic amines, anthracene derivatives, anthracinone derivatives, coumarin derivatives, thioxanthone derivatives, phthalocyanine derivatives, aromatic ketones such as benzophenone, xanthone, thioxanthone, Michler ketone, 9,10-phenanthraquinone, and derivatives thereof. be able to.
The photopolymerization initiator and the sensitizer may be contained in a state of being bound to the (meth) acrylic (co) polymer. As a method for binding the photopolymerization initiator and the sensitizer to the (meth) acrylic (co) polymer, the same method as in the case of binding the cross-linking agent to the (meth) acrylic (co) polymer is adopted. can do.

The content of the photopolymerization initiator is not particularly limited, and is typically 0.1 or more and 10 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic (co) polymer, particularly 0. It is particularly preferable to make adjustments at a ratio of 2 parts by mass or more or 5 parts by mass or less, of which 0.5 parts by mass or more or 3 parts by mass or less. However, this range may be exceeded in balance with other factors.

(Antioxidant)
In addition to the above, the composition may contain an antioxidant, if necessary.
Examples of the antioxidant include 2,2'-methylenebis (4-methyl-6-t-butylphenol), hexamethylene glycol-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamate), and the like. Tetrakiss [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamete)] methane, triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy-benzyl) benzene, n-octadecyl-3- (4'-hydroxy-3', 5) '-Di-t-butylphenol) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidene-bis- (6-t-butyl-3-methyl-phenol) Examples thereof include hindered phenol-based antioxidants such as, and various antioxidants such as sulfur-based and amine-based.

(Other ingredients)
Further, the present composition may appropriately contain known components contained in ordinary pressure-sensitive adhesive compositions. For example, light stabilizers, ultraviolet absorbers, metal inactivating agents, rust inhibitors (excluding the above-mentioned metal corrosion inhibitors), antiaging agents, antistatic agents, hygroscopic agents, foaming agents, defoaming agents, inorganic substances. Various additives such as particles, viscosity modifiers, antistatic resins, photosensitizers, and fluorescent agents, and reaction catalysts (tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, etc.) are appropriately contained. It is possible.

(Adhesive composition adjustment)
The pressure-sensitive adhesive composition (the present composition) used for the present pressure-sensitive adhesive sheet is a (meth) acrylic (co) polymer, 1,2,3-triazole and, if necessary, other components, for example, a phosphite ester compound. It is obtained by mixing a predetermined amount of each of a cross-linking agent and the like.
The mixing method thereof is not particularly limited, and the mixing order of each component is not particularly limited. Further, a heat treatment step may be added at the time of producing the present composition, and in this case, it is desirable to mix each component of the present composition in advance and then perform the heat treatment. A masterbatch made by concentrating various mixed components may be used.

Further, the apparatus for mixing is not particularly limited, and for example, a universal kneader, a planetary mixer, a Banbury mixer, a kneader, a gate mixer, a pressurized kneader, a three-roll, and a two-roll can be used. If necessary, it may be mixed with a solvent. Further, the present composition can be used as a solvent-free system containing no solvent. By using it as a solvent-free system, it is possible to have an advantage that the solvent does not remain and the heat resistance and the light resistance are improved.

Further, this composition is prepared as a composition containing a monomer component constituting a (meth) acrylic (co) polymer, 1,2,3-triazole, a photopolymerization initiator and other optional components, and this is made conductive. When used as an adhesive sheet for a member, it can also be used so that a (meth) acrylic (co) polymer is produced by irradiating with light to promote a polymerization reaction.

<Form of adhesive sheet for conductive member>
This adhesive sheet is not only used by directly applying the composition to an adherend to form a sheet, but also an adhesive sheet with a release film formed into a single-layer or multi-layer sheet on a release film. It can also be.
Examples of the material of the release film include a polyester film, a polyolefin film, a polycarbonate film, a polystyrene film, an acrylic film, a triacetyl cellulose film, a fluororesin film and the like. Among these, polyester film and polyolefin film are particularly preferable.

The thickness of the release film is not particularly limited. Among them, for example, from the viewpoint of processability and handleability, it is preferably 25 μm to 500 μm, and more preferably 38 μm or more or 250 μm or less, and more preferably 50 μm or more or 200 μm or less.

The pressure-sensitive adhesive sheet may be molded by directly extruding the composition or by injecting the composition into a mold without using an adherend or a release film as described above. I can. Furthermore, the present composition can be directly filled between members such as conductive members to form an adhesive sheet.

<Physical characteristics of adhesive sheet for conductive members>
(Corrosion prevention effect on the conductive layer of the conductive member)
The present adhesive sheet has corrosion resistance to a conductive member, particularly a conductor pattern formed of a transparent conductive layer or a metal material including copper. Therefore, the rate of change [((Ω / Ω0) -1) × 100] of the ITO resistance value measured by the following methods (1) and (2) can be set to less than 5%, especially less than 3%. Further, the rate of change [((Ω / Ω0) -1) × 100] of the copper resistance value measured by the following methods (3) to (4) is less than 20%, particularly less than 10%, and further less than 5%. In particular, it can be less than 3%.

(1) Evaluation of forming an adhesive composition for a conductive member (this composition) into a sheet having a thickness of 150 μm to form an adhesive sheet, and forming ITO wiring made of indium oxide (ITO) on a glass substrate. The adhesive sheet is attached to the ITO glass substrate for use to produce ITO wiring with an adhesive sheet.

(2) The resistance value (Ω0) of the ITO wiring in the ITO wiring with the adhesive sheet at room temperature is measured in advance, and the ITO wiring with the adhesive sheet is stored in an environment of 65 ° C. and 90% RH for 500 hours. The resistance value (Ω) of the ITO wiring in the ITO wiring with an adhesive sheet after storage is measured.

(3) The pressure-sensitive adhesive composition for conductive members (this composition) is formed into a sheet having a thickness of 150 μm to form an adhesive sheet, and copper wiring is formed on the glass substrate on the evaluation copper glass substrate. A copper wiring with an adhesive sheet is manufactured by laminating the adhesive sheets.

(4) The resistance value (Ω0) of the copper wiring in the copper wiring with the adhesive sheet at room temperature is measured in advance, and the copper wiring with the adhesive sheet is stored in the environment of 65 ° C. and 90% RH for 500 hours. The resistance value (Ω) of the copper wiring in the copper wiring with an adhesive sheet after storage is measured.

(transparency)
The pressure-sensitive adhesive sheet is preferably optically transparent. That is, it is preferably a transparent adhesive sheet. Here, "optically transparent" is intended to have a total light transmittance of 80% or more, preferably 85% or more, and more preferably 90% or more.

(thickness)
The thickness of the pressure-sensitive adhesive sheet is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more or 400 μm or less, and particularly preferably 20 μm or more or 350 μm or less.

<Use of adhesive sheet for conductive members>
This adhesive sheet is, for example, an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, for example, a plasma display (PDP), a liquid crystal display (LCD). In an image display device using an image display panel such as an organic EL display (OLED), an inorganic EL display, an electrophoretic display (EPD), and an interference modulation display (IMOD), each component, particularly a conductive member, and particularly a transparent conductive member. It is suitable for laminating conductive members having a conductor pattern formed of a layer and / or a metal material containing copper. It is also suitable for laminating a conductive member including a transparent conductive layer containing ITO or IGZO and / or a transparent conductive layer having a conductor pattern formed of a metal material containing copper or silver.

<Conductive member laminate>
The conductive member laminate of the present invention (hereinafter, also abbreviated as "the present laminate") can be obtained by laminating the present adhesive sheet with a conductive member, for example, a conductive layer surface of a transparent conductive layer. ..
The laminate may have a structure in which at least one of the pressure-sensitive adhesive layer surfaces of the pressure-sensitive adhesive sheet and the conductive layer surface of the transparent conductive layer are bonded together.
When the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, the laminate may have a structure in which both pressure-sensitive adhesive layer surfaces of the pressure-sensitive adhesive sheet and the conductive layer surface of the transparent conductive layer are bonded to each other.

In the transparent conductive layer, an insulating protective film (passion film) made of an olefin polymer, a urethane polymer, an epoxy polymer, an acrylic polymer, a silicone polymer, inorganic glass or the like is formed so as to cover the conductive layer surface of the conductive film. It may have been done.
In this case, the present adhesive sheet is not directly bonded to the transparent conductive layer surface (it is not in direct contact with the transparent conductive layer surface). In this pressure-sensitive adhesive sheet, even if a component derived from the present composition (particularly an acid component) permeates and reaches the transparent conductive layer from the insulating film, the transparent conductive layer is corroded by the action of 1,2,3-triazole. It can be prevented. In particular, 1,2,3-triazole has high water solubility and easily moves to the transparent conductive layer when the present adhesive sheet absorbs moisture in a moist heat environment, so that an excellent metal corrosion prevention effect can be exhibited.
As described above, according to this adhesive sheet, regardless of the presence or absence of the insulating protective film, not only the discoloration and deterioration of the adhesive layer due to the metal ions of the adherend but also the excellent metal corrosion prevention effect on the adherend can be obtained. Can be done.

This laminated body obtained by laminating with the conductive layer surface can be suitably used for a touch panel. Examples of the touch panel include a resistance film method, a capacitance method, an electromagnetic induction method, and the like, and the capacitance method is preferable.

The transparent conductive layer may be any one having a conductive layer on at least one surface layer, and examples thereof include a transparent conductive layer in which a conductive substance is provided on the surface layer of a transparent base material by vapor deposition, sputtering, coating, or the like.
The conductive material used for the conductive layer of the transparent conductive layer is not particularly limited, and specifically, indium oxide, indium-gallium-zinc composite oxide, tin-doped indium oxide (ITO), zinc oxide, gallium oxide, and titanium oxide. In addition to metal oxides such as silver, copper, molybdenum, and metal materials such as aluminum can be mentioned. Among them, tin-doped indium oxide (ITO) and indium-gallium-zinc composite oxide (IGZO), which are excellent in transparency, are preferably used. Further, copper and silver can also be preferably used from the viewpoint of excellent conductivity. The base material on which the conductive substance is patterned in the transparent conductive layer is not particularly limited, and examples thereof include glass and a resin film.

The transparent conductive layer typically has a conductive layer on at least one surface. Further, typically, a conductor pattern (wiring pattern) containing copper or silver as a main component is formed on the transparent conductive layer so as to route around the peripheral portion. Since 1,2,3-triazole has high corrosion resistance and reliability with respect to copper, the present pressure-sensitive adhesive sheet containing it is particularly suitable for a conductive member having a conductor pattern formed of a metal material containing copper. It can be suitably used.

Specific examples of the other laminated body include, for example, a release film / main adhesive sheet / touch panel, a release film / main adhesive sheet / protective panel, a release film / main adhesive sheet / image display panel, and an image display panel / book. Adhesive sheet / touch panel, image display panel / main adhesive sheet / protective panel, image display panel / main adhesive sheet / touch panel / main adhesive sheet / protective panel, polarizing film / main adhesive sheet / touch panel, polarizing film / main adhesive sheet / touch panel / This adhesive sheet / Protective panel and the like can be mentioned. Further, in the above configuration, all configurations in which the conductive layer intervenes between the present adhesive sheet and a member such as a touch panel, a protective panel, an image display panel, and a polarizing film adjacent thereto can be mentioned. However, the present invention is not limited to these laminated examples.
The touch panel includes a structure having a touch panel function built into the protective panel and a structure having a touch panel function built into the image display panel.

<Image display device>
The image display device of the present invention (hereinafter, also abbreviated as "the device") has at least the present laminate, an image display panel, and a surface protection panel as constituent members.

More specifically, the image display device having a structure in which the present laminate obtained by laminating the present adhesive sheet with the conductive layer surface of the transparent conductive layer is interposed between the image display panel and the surface protection panel is mentioned. Can be done. At this time, the adhesive sheet can also be used on the image display panel side.

As the material of the surface protection panel, in addition to glass, acrylic resin, polycarbonate resin, alicyclic polyolefin resin such as cycloolefin polymer, styrene resin, polyvinyl chloride resin, phenol resin, melamine resin, etc. It may be a plastic such as an epoxy resin.

The image display panel is composed of other optical films such as a polarizing film and other retardation films, a liquid crystal material, and a backlight system (usually, the adherend surface of the composition or the adhesive article to the image display panel is an optical film. There are STN method, VA method, IPS method and the like depending on the control method of the liquid crystal material, but any method may be used.

As the image display device, for example, an image display device such as a liquid crystal display, an organic EL display, an inorganic EL display, an electronic paper, a plasma display, and a microelectromechanical system (MEMS) display can be configured.

<Explanation of words>
When expressed as "X to Y" (X and Y are arbitrary numbers) in the present specification, they mean "X or more and Y or less" and "preferably larger than X" or "preferably Y". It also includes the meaning of "smaller".
Further, when expressed as "X or more" (X is an arbitrary number) or "Y or less" (Y is an arbitrary number), it means "preferably larger than X" or "preferably less than Y". Intention is also included.

Generally, a "sheet" is a product that is thin by definition in JIS, and its thickness is small for its length and width, and is flat. Generally, a "film" is thicker than its length and width. A thin, flat product with an extremely small size and an arbitrarily limited maximum thickness, which is usually supplied in the form of a roll (Japanese Industrial Standards JISK6900). However, since the boundary between the sheet and the film is not fixed and it is not necessary to distinguish between the two in the present invention, in the present invention, even if the term "film" is used, the term "sheet" is included and is referred to as "sheet". Even if it is, it shall include "film".

Hereinafter, it will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

<(Meta) acrylic (co) polymer>
The following (meth) acrylic (co) polymers were used.
A-1: Copolymer consisting of 76 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of vinyl acetate and 4 parts by mass of acrylic acid (mass average molecular weight 400,000)
A-2: A copolymer consisting of 81 parts by mass of butyl acrylate, 15 parts by mass of methyl methacrylate and 4 parts by mass of acrylic acid (mass average molecular weight 200,000).

<Example 1>
[Example 1-1]
For 1 kg of (meth) acrylic (co) polymer (A-1), 3 g of 1,2,3-triazole (manufactured by Otsuka Chemical Co., Ltd.) as a metal corrosion inhibitor and 4-methylbenzophenone as a photopolymerization initiator. 15 g of a mixture of 2,4,6-trimethylbenzophenone (manufactured by Lamberti, trade name "EzaCure TZT") was added and uniformly mixed to obtain a resin composition for a pressure-sensitive adhesive layer.

Two polyethylene terephthalate films obtained by peeling off the resin composition for the pressure-sensitive adhesive layer (manufactured by Mitsubishi Plastics, trade name "Diafoil MVR", thickness 100 μm, and manufactured by Mitsubishi Plastics, trade name "Diafoil MRQ", It was sandwiched between (thickness 75 μm) and shaped into a sheet so that the thickness of the pressure-sensitive adhesive sheet was 150 μm, to prepare a pressure-sensitive adhesive sheet laminate. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 1.

[Example 1-2]
For 1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor and UV curable resin propoxydated pentaerythritol triacrylate as a cross-linking agent (Shin-Nakamura Kogyo Co., Ltd.) 20 g of the company, trade name "ATM-4PL") and 15 g of a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (manufactured by Lamberti, trade name "Ezacure TZT") as a photopolymerization initiator are added uniformly. The mixture was mixed to obtain a resin composition for a pressure-sensitive adhesive layer.

Next, the resin composition for the pressure-sensitive adhesive layer was molded into a sheet shape on a stripped polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., trade name "Diafoil MRV", thickness 100 μm) so as to have a thickness of 150 μm. After that, a stripped polyethylene terephthalate film (manufactured by Mitsubishi Resin Co., Ltd., trade name "Diafoil MRQ", thickness 75 μm) was coated to prepare an adhesive sheet laminate. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 1.

[Example 1-3]
A pressure-sensitive adhesive sheet laminate was prepared in the same manner as in Example 1-2 except that 5 g of 1,2,3-triazole was used as the metal corrosion inhibitor. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 1.

[Comparative Example 1-1]
A pressure-sensitive adhesive sheet laminate was prepared in the same manner as in Example 1-1 except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 1.

[Comparative Example 1-2]
An adhesive sheet laminate was prepared in the same manner as in Example 1-1 except that 5 g of benzotriazole (manufactured by Johoku Chemical Co., Ltd., trade name "BT120") was used instead of 1,2,3-triazole as a metal corrosion inhibitor. bottom. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 1.

[Comparative Example 1-3]
As a metal corrosion inhibitor, 5 g of triltriazole (a mixture of 4-methylbenzotriazole and 5-methylbenzotriazole) (trade name "SEETEC TT-R" manufactured by Cipro Chemical Co., Ltd.) is used instead of 1,2,3-triazole. Except for the above, a pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 1-1. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 1.

[Comparative Example 1-4]
Example 1-1 except that 5 g of 2,5-dimercapto-1,3,4-thiadiazole (manufactured by Toyobo Co., Ltd., trade name "MTD") is used instead of 1,2,3-triazole as a metal corrosion inhibitor. In the same manner as above, an adhesive sheet laminate was produced. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 1.

<Various evaluations>
(1) Corrosion resistance reliability ITO with a thickness of 1300 Å and copper with a thickness of 3000 Å so as to make 10.5 reciprocations on a glass substrate (60 mm × 45 mm) with a line width of 70 μm, a line length of 46 mm, and a line spacing of 30 μm. A reciprocating line of a metal film formed by laminating the films in this order is formed, and 2 mm square squares are formed at both ends of the reciprocating line to form a copper pattern (length of about 97 cm) to evaluate corrosion resistance reliability. A copper glass substrate for use was prepared (see FIG. 1 (A)).

Peel off the release film on one side of the adhesive sheet laminate (adhesive sheet thickness 150 μm) produced in the above Examples and Comparative Examples, and polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4100”) on the exposed surface. , 125 μm) was attached with a hand roller. Next, after cutting out the adhesive sheet with PET film to a size of 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. 1 (B), corrosion resistance is reliable so as to cover the reciprocating line of the metal film. The adhesive sheet is attached to the evaluation copper glass substrate by a hand roller, and the integrated light amount having a wavelength of 365 nm is 3000 mJ / in Examples 1-1 and Comparative Examples 1-1 to 1-4 via a PET film. In cm ² , Examples 1-2 and 1-3 are ^{irradiated with ultraviolet rays at 2000 mJ / cm 2} with a high-pressure mercury lamp and cross-linked with ultraviolet rays to obtain a sample for corrosion resistance evaluation (copper wiring with adhesive sheet). It was prepared (see FIG. 1 (D)).

The resistance value (Ω0) of the copper wiring in this corrosion resistance reliability evaluation sample (copper wiring with an adhesive sheet) at room temperature was measured in advance.

On the other hand, the corrosion resistance evaluation sample (copper wiring with adhesive sheet) is stored for 500 hours in a 65 ° C. and 90% RH environment, and after storage, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) is stored. The resistance value (Ω) of the copper wiring in was measured.

Then, the rate of change (%) [((Ω / Ω0) -1) × 100] of the copper resistance value, that is, the resistance value between the line ends was calculated and shown as “resistance value change” in Table 1.

Regarding the corrosion resistance reliability, those having a resistance value change rate of 20% or more were judged as "x (poor)", and those with a resistance value of less than 20% were judged as "○ (good)". The results are shown in Table 1.

(2) Foaming reliability Peel off the release film on one side of the adhesive sheet laminate (thickness 150 μm) produced in the examples and comparative examples, and put it on a soda lime glass plate (150 × 200 mm, thickness 0.55 mm) as a hand roll. And pasted together. Further, the remaining release film was peeled off, and the chemically strengthened glass plate (180 × 220 mm, thickness 0.6 mm) was bent and bonded by hand roll.

Next, the bonded product was autoclaved in an environment of 60 ° C. and 0.2 MPa for 20 minutes. This sample was subjected to a metal halide lamp irradiation device (manufactured by Ushio Denki Co., Ltd., type UVC-0516S1, lamp UVL-8001M3-N), and a belt conveyor ^{was used so that the irradiation amount at a wavelength of 365 nm was 3000 mJ / cm 2 per irradiation.} After adjusting the speed and irradiance and irradiating 15 times, the change in appearance was observed.

Regarding the foam resistance reliability, when the appearance was observed, those having no change from those before the irradiation with ultraviolet rays were judged as "○ (good)", and those with bubbles were judged as "x (poor)". The results are shown in Table 1.

(3) UV curing characteristics (storage elastic modulus before UV curing G')
The storage elastic modulus before UV curing was measured by laminating the adhesive sheets prepared in Examples and Comparative Examples to a thickness of 1 to 2 mm and punching them into a circle with a diameter of 20 mm. Using the company's "MARS"), adhesive jig: Φ25mm parallel plate, strain: 0.5%, frequency: 1Hz, temperature: -50 to 200 ° C, temperature rise rate: 3 ° C / min, -50 ° C The dynamic storage elastic modulus G'up to ~ 200 ° C. was measured, and the storage elastic modulus value at 125 ° C. was read. The results are shown in Table 1.

(Store elastic modulus G'after UV curing)
The storage elastic modulus after UV curing was measured as follows.
The pressure-sensitive adhesive sheets produced in Examples and Comparative Examples were irradiated with ultraviolet rays with a high-pressure mercury lamp via a PET film and crosslinked with ultraviolet rays. At this time, for Examples 1-1 and Comparative Examples 1-1 to 1-4, irradiation was performed so that the integrated light amount at a wavelength of 365 nm was 3000 mJ / cm ^2, and Examples 1-2 and 1-3 were laminated. Irradiation was performed so that the amount of light was 2000 mJ / cm ^2. The adhesive sheets crosslinked with ultraviolet rays in this way were laminated to a thickness of 1 to 2 mm, and punched into a circle having a diameter of 20 mm was used as a measurement sample.
Using a rheometer (manufactured by Eiko Seiki Co., Ltd., trade name "MARS"), adhesive jig: Φ25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: -50 to 200 ° C, temperature rise rate: 3 The dynamic storage elastic modulus G'of the measurement sample from -50 ° C to 200 ° C was measured at ° C./min, and the storage elastic modulus after UV curing was obtained by reading the storage elastic modulus value at 125 ° C. .. The results are shown in Table 1.

Regarding the UV curing characteristics, comparing the storage elastic modulus G'before UV curing and the storage elastic modulus G'after UV curing, the value after curing is "○ (good)", and the value is almost changed to the value. Those without "x" were judged as "x (poor)". The results are shown in Table 1.

(Evaluation results)
The adhesive sheet of Examples 1-1 to 1-3 contains 1,2,3-triazole as a metal corrosion inhibitor, so that the resistance value of the copper wiring does not change much and the corrosion resistance is excellent. there were. In addition, the foaming reliability and the ultraviolet curing characteristics were also good.

On the other hand, Comparative Example 1-1 did not contain a metal corrosion inhibitor and was inferior in corrosion resistance and reliability.
Comparative Example 1-2 contained benzotriazole as a metal corrosion inhibitor, but was inferior in foaming reliability due to the characteristics of benzotriazole.
Comparative Examples 1-3 contained tolyltriazole as a metal corrosion inhibitor, but were inferior in foaming reliability due to the characteristics of tolyltriazole.
Comparative Example 1-4 contains dimercaptothiadiazole as a metal corrosion inhibitor, but since dimercaptothiadiazole absorbs ultraviolet rays, the pressure-sensitive adhesive sheet is inferior in ultraviolet curing characteristics.

From the above results, 1,2,3-triazole has a melting point of about 20 ° C. and is almost liquid at room temperature, so that it can be easily added to the pressure-sensitive adhesive in the actual manufacturing process of the pressure-sensitive adhesive sheet, and it is also pressure-sensitive. It was also found to be excellent in dispersibility in the main agent.
In addition, 1,2,3-triazole has high water solubility and easily moves to the surface of the metal layer (copper wiring) when the adhesive sheet absorbs moisture in a moist heat environment, so that it exhibits an excellent metal corrosion prevention effect. It also became clear that it could be done.
It was also clarified that 1,2,3-triazole does not impair UV curing characteristics because it does not absorb at a spectrophotometric intensity of 300 to 400 nm.
As described above, it has been found that 1,2,3-triazole has excellent properties as compared with the conventional metal corrosion inhibitor, and is particularly effective when used for an adhesive sheet for a conductive member.

<Example 2>
[Example 2-1]
200 g of propoxylated pentaerythritol polyacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "ATM-4PL") as a cross-linking agent for 1 kg of (meth) acrylic (co) polymer (A-1), photopolymerization started. As an agent, 10 g of a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (manufactured by Lamberti, trade name "Ezacure TZT") was added and uniformly mixed to obtain a resin composition for an intermediate layer.

Two polyethylene terephthalate films (manufactured by Mitsubishi Plastics, trade name "Diafoil MRF", thickness 75 μm, and Mitsubishi Plastics, trade name "Diafoil MRT", thick) obtained by peeling off the resin composition for the intermediate layer. It was sandwiched between them (38 μm) and shaped into a sheet so that the thickness of the pressure-sensitive adhesive sheet was 80 μm, to prepare a resin sheet (α) for an intermediate layer.

For 1 kg of (meth) acrylic (co) polymer (A-1), 1.5 g of 1,2,3-triazole as a metal corrosion inhibitor and tris (2,4) phosphite as a phosphite ester compound. -Di-t-butylphenyl) (BASF, trade name "Irgafos 168") 5 g and a mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone as a photopolymerization initiator (Lamberti, trade name " EzaCure TZT ”) 15 g was added and uniformly mixed to obtain a resin composition for a pressure-sensitive adhesive layer.

Two polyethylene terephthalate films (manufactured by Mitsubishi Plastics, trade name "Diafoil MRV", thickness 100 μm, and Mitsubishi Plastics, trade name "Diafoil MRT") obtained by peeling off the fat composition for the pressure-sensitive adhesive layer. (Thickness 38 μm), and shaped into a sheet so that the thickness of the pressure-sensitive adhesive sheet is 35 μm, to prepare a resin sheet (β) for the pressure-sensitive adhesive layer.

Further, two polyethylene terephthalate films (manufactured by Mitsubishi Plastics, trade name "Diafoil MRQ", thickness 75 μm, manufactured by Mitsubishi Plastics Co., Ltd., trade name "Diafoil") obtained by peeling off the fat composition for the pressure-sensitive adhesive layer. It was sandwiched between MRT (thickness 38 μm) and shaped into a sheet so that the thickness of the pressure-sensitive adhesive sheet was 35 μm, to prepare a resin sheet (β') for the pressure-sensitive adhesive layer.

The PET films on both sides of the intermediate layer sheet (α) are sequentially peeled off and removed, and the PET films on one side of the adhesive layer resin sheet (β) and (β') are peeled off so that the exposed adhesive surface is intermediate. The layered sheet (β) was sequentially bonded to both surfaces to prepare a laminated body composed of (β) / (α) / (β').

Through the PET film remaining on the surfaces of (β) and (β'), ultraviolet rays are irradiated with a high-pressure mercury lamp so ^{that the integrated light amount at a wavelength of 365 nm is 2000 mJ / cm 2, and (α), (β) and} (Β') was crosslinked with ultraviolet rays to prepare a pressure-sensitive adhesive sheet laminate (thickness 150 μm). The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 2.

[Example 2-2]
For 1 kg of (meth) acrylic (co) polymer (A-2), 3 g of 1,2,3-triazole as a metal corrosion inhibitor and tridecyl phosphite as a phosphite ester compound (manufactured by Adeca, trade name). "Adecastab 3010") 3 g, pentaerythritol tri and tetraacrylate (Toa Synthetic Co., Ltd., "Aronix M-306") 20 g as a cross-linking agent, and 1-hydroxy-cyclohexylphenylketone (BASF Co., Ltd., Irgacure) as a photopolymerization initiator. 184) 10 g was added and uniformly mixed to obtain a resin composition for a pressure-sensitive adhesive layer.

Next, the resin composition for the pressure-sensitive adhesive layer was formed into a sheet on a stripped polyethylene terephthalate film (manufactured by Mitsubishi Plastics, Diafoil MRV, thickness 100 μm) so as to have a thickness of 150 μm, and then peeled. The polyethylene terephthalate film (manufactured by Mitsubishi Plastics, trade name "Diafoil MRQ", thickness 75 μm) was coated. An adhesive sheet laminate is obtained by irradiating the resin composition for the pressure-sensitive adhesive layer with ultraviolet rays with a high-pressure mercury lamp so that the integrated light amount at a wavelength of 365 nm is 1000 mJ / cm ^{2 through the stripped polyethylene terephthalate film.} Was produced. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 2.

[Example 2-3]
As a phosphite ester compound, 3,9-bis (decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (manufactured by Johoku Chemical Co., Ltd., trade name "JPE-10") A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-2 except that 3 g was used. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 2.

[Comparative Example 2-1]
1,2,3-Triazole as a metal corrosion inhibitor and Tris phosphite (2,4-di-t-butylphenyl) as a phosphite ester compound (manufactured by BASF, trade name "Irgafos 168") The various evaluations described below were performed on the pressure-sensitive adhesive sheet laminate in which the pressure-sensitive adhesive sheet laminate was prepared in the same manner as in Example 2-1 except that the pressure-sensitive adhesive sheet laminate was not added. The results are shown in Table 2.

[Comparative Example 2-2]
A pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-1 except that 1,2,3-triazole as a metal corrosion inhibitor was not added. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 2.

[Comparative Example 2-3]
As a metal corrosion inhibitor, 1.5 g of benzotriazole (manufactured by Johoku Chemical Co., Ltd., trade name "BT120") is added instead of 1,2,3-triazole, except that a phosphite ester compound is not added. An adhesive sheet laminate was produced in the same manner as in Example 2-1. The adhesive sheet laminate was evaluated in various ways as described below. The results are shown in Table 2.

<Various evaluations>
(1) Anti-oxidation deterioration resistance Indium oxide (ITO) reciprocates on a glass substrate (60 mm × 45 mm) so as to reciprocate 10.5 on a glass substrate (60 mm × 45 mm) with a thickness of 150 to 200 Å, a line width of 70 μm, a line length of 46 mm, and a line spacing of 30 μm. Along with forming the wire, a 2 mm square square made of ITO was formed at both ends of the reciprocating wire to form an ITO pattern (length of about 97 cm), and an ITO glass substrate for evaluation of oxidative deterioration prevention was produced (FIG. 1 (A)).

Peel off the release film on one side of the adhesive sheet laminate (thickness 150 μm) produced in the above Examples and Comparative Examples, and hand a PET film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4100”, 125 μm) on the exposed surface. It was attached with a roller. Next, after cutting out the adhesive sheet with PET film to 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. 1 (B), the oxidation deterioration prevention property evaluation is performed so as to cover the reciprocating line of ITO. The adhesive sheet was attached to an ITO glass substrate for use with a hand roller to prepare a sample for evaluation of oxidative deterioration prevention property (ITO wiring with an adhesive sheet) (see FIG. 1 (C)).

The resistance value (Ω0) of the ITO wiring at room temperature in this oxidative deterioration prevention evaluation sample (ITO wiring with an adhesive sheet) was measured in advance.

On the other hand, the oxidative deterioration prevention evaluation sample (ITO wiring with adhesive sheet) is stored for 500 hours in a 65 ° C. 90% RH environment, and after storage, the oxidative deterioration prevention evaluation sample (ITO wiring with adhesive sheet) is stored. ), The resistance value (Ω) of the ITO wiring was measured.

Then, the rate of change (%) [((Ω / Ω0) -1) × 100] of the ITO resistance value, that is, the resistance value between the line ends was calculated and shown as “resistance value change” in Table 2.

Regarding the oxidative deterioration prevention property, those having a resistance value change rate of 5% or more were judged to be "x (poor)", and those having a resistance value of less than 5% were judged to be "○ (good)". The results are shown in Table 2.

(2) Corrosion resistance reliability ITO with a thickness of 1300 Å and copper with a thickness of 3000 Å so as to make 10.5 reciprocations on a glass substrate (60 mm × 45 mm) with a line width of 70 μm, a line length of 46 mm, and a line spacing of 30 μm. A reciprocating line of a metal film formed by laminating the films in this order is formed, and 2 mm square squares are formed at both ends of the reciprocating line to form a copper pattern (length of about 97 cm) to evaluate corrosion resistance reliability. A copper glass substrate for use was prepared (see FIG. 1 (A)).

Peel off the release film on one side of the adhesive sheet laminate (thickness 150 μm) produced in the above Examples and Comparative Examples, and hand a PET film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4100”, 125 μm) on the exposed surface. It was attached with a roller. Next, after cutting out the adhesive sheet with PET film to 52 mm × 45 mm, the remaining release film is peeled off, and as shown in FIG. 1 (B), corrosion resistance is reliable so as to cover the reciprocating line of the metal film. An adhesive sheet was attached to the evaluation copper glass substrate with a hand roller to prepare a sample for corrosion resistance evaluation (copper wiring with an adhesive sheet) (see FIG. 1 (D)).

The resistance value (Ω0) of the copper wiring in this corrosion resistance reliability evaluation sample (copper wiring with an adhesive sheet) at room temperature was measured in advance.

On the other hand, the corrosion resistance evaluation sample (copper wiring with adhesive sheet) is stored for 500 hours in a 65 ° C. and 90% RH environment, and after storage, the corrosion resistance reliability evaluation sample (copper wiring with adhesive sheet) is stored. The resistance value (Ω) of the copper wiring in was measured.

Then, the rate of change (%) [((Ω / Ω0) -1) × 100] of the copper resistance value, that is, the resistance value between the line ends was calculated and shown as “resistance value change” in Table 2.

Regarding the corrosion resistance reliability, those having a resistance value change rate of 20% or more were judged as "x (poor)", and those with a resistance value of less than 20% were judged as "○ (good)". The results are shown in Table 2.

(Evaluation results)
The pressure-sensitive adhesive sheet of Examples 2-1 to 2-3 contains 1,2,3-triazole as a metal corrosion inhibitor and further contains a phosphite ester to change the resistance value of both ITO wiring and copper wiring. It was excellent in corrosion resistance reliability and oxidative deterioration prevention property.

On the other hand, Comparative Example 2-1 did not contain both the phosphite ester compound and the metal corrosion inhibitor, and was inferior in corrosion resistance reliability and oxidative deterioration inhibitory property.
In Comparative Example 2-2, since the metal corrosion inhibitor was not contained, the corrosion of the copper wiring was particularly remarkable.
Comparative Example 2-3 did not contain a phosphite ester compound and was inferior in oxidative deterioration prevention property to ITO wiring.

The pressure-sensitive adhesive sheet for a conductive member of the present invention has corrosion resistance and reliability for a conductive member (typically a transparent conductive layer and / or a conductive member having a conductor pattern formed of a metal material containing copper or silver). Since it can have foaming reliability, it can be used as a suitable pressure-sensitive adhesive sheet for bonding various conductive members. In particular, it can be suitably used as an adhesive sheet for an image display device having a touch panel.

Claims (12)

(Meth) have a pressure-sensitive adhesive layer including the pressure-sensitive adhesive composition containing an acrylic copolymer and 1,2,3-triazole, the adhesive composition is a composition having a photocurable conductive member Adhesive sheet for. The pressure-sensitive adhesive sheet for a conductive member according to claim 1, wherein the pressure-sensitive adhesive composition contains a phosphite ester compound. The phosphite ester compound comprises any one or more selected from an aliphatic phosphite ester, an aromatic phosphite ester, and a phosphite ester having an aliphatic ester group and an aromatic ester group. The adhesive sheet for a conductive member according to claim 1 or 2. The pressure-sensitive adhesive sheet for a conductive member according to any one of claims 1 to 3, wherein the (meth) acrylic copolymer contains a carboxyl group-containing monomer as a constituent unit. The pressure-sensitive adhesive sheet for a conductive member according to claim 4, wherein the (meth) acrylic copolymer contains a carboxyl group-containing monomer in an amount of 1.2 to 15% by mass. The pressure-sensitive adhesive sheet for a conductive member according to any one of claims 1 to 5 , wherein the pressure-sensitive adhesive composition contains a cross-linking agent. The pressure-sensitive adhesive sheet for a conductive member according to any one of claims 1 to 6 , wherein the conductive member has a transparent conductive layer. The pressure-sensitive adhesive sheet for a conductive member according to claim 7 , wherein the transparent conductive layer has an insulating protective film. The conductive member according to any one of claims 1 to 8 , wherein the conductive member has a transparent conductive layer containing tin-doped indium oxide and / or a conductor pattern formed of a metal material containing copper. Adhesive sheet. A conductive member laminate having a structure in which the adhesive sheet for a conductive member according to any one of claims 1 to 9 is bonded to the conductive member. An image display device including the conductive member laminate, the image display panel, and the surface protection panel according to claim 10. (Meta) A pressure-sensitive adhesive composition for a photocurable conductive member containing an acrylic copolymer and 1,2,3-triazole.

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